Anthracene compound and process of making same.



Patented April 18, 1905.

UNITED STATES PATENT @FFlCEe MANNHEIM, GEltUANL',

ASSIGNORS TO BADISOI'IE ANILIN & SODA FABRIK, OF LUDWIGSHAFEN'ON-TllEltllINE, GERMANY, A CORPORA- TION OF BADEN.

ANTHRACENE COMPOUND AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 787,859, dated April 18, 1905.

Application tiled January 7, 1905. Serial No. 240,099.

To rl// lr/lrmt 1'1" lit/1y (POUR/W711.

Be it known that we, ROLAND lTEINRICII ScnoLL. pro'lcssor ot chemistry and doctor ot philosophy, a subject ol the King of Bavaria 1 and ot the Grand Duke of Baden, residiin at 5 r liarlsruhe, and Oscar: BALLY, doctor of phi losophy and chemist, a citizen of the Swiss Republic, residing at Mannheim, in the Grand Duchy of Baden, Germany,have invented new [0 and uselul improvements in new I\nthracene Compounds and Processes tor Producing the Same, oi which the following is a specification.

Our invention relates to the production of new products ol' the anthracene series which are of use for the preparation of new coloring matters.

in the specification of the application for Letters Patent Serial No. 233,161, filed November 17, 1904, is described the production of new products of the anthraccne series by condensing a beta-amido-anthraquinone or a sullo-acid of a beta-amido-anthraquinone with glycerin in the presence o'l SLil'illl'lC acid.

structural Formula:

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The anthracene compounds which can be used according to our invention include anthracene itself, its meso-oxy and hydroXy derivatives, and also the sulto-acids of any of? these compounds. As examples, we mention the following compounds: anthraquinone, anthranol, oxanthranol, the anthracene sul'lo-acids, and anthraquinone sul'toacids. Of course instead of" anthracene its lu'nnologucs may be employed. The condensation, generally takes place on heating together the anthracene body and the glyc erin; but in most cases the presence of sulluric acid or of another body or bodies which may assist in the condensation is advisable. After the condensation the melt is poured into water or ice and water, whereupon the products obtained from the unsul'lonated compounds are generally precipitated,where as those obtained from the sullonated anthracene compounds are more soluble in water, but can be precipitated by the addition of common salt to the solution. These condensation products on being melted with caustic alkali yield violet-blue loringmat ters possessing general characteristics similar to those of indanthrene-that to say, they cannot be used directly for dyeing, because they are insoluble in water-but on treatment with an alkaline reducing agentfor instance, alkaline hyd rosulfitethey yield soluble lcuco compounds which dye vegetable fiber shades which on washing with water become fixed, being reconverted into the insoluble coloring-matter. The condensation products are all characterized by their solubility in concentrated sulfuric acid, in which they yield from orange to green solutions with green to red fluorescence.

The following examples will serve to i'urther illustrate the nature of our invention, whicleliowever, is not limited to these examples. The parts are by weight.

Example 1: Introduce one (1) part of anthracene (containing about ninety-eight (98) per cent. of the pure compound) into thirty (30) parts of sul'l'uric acid (containing about eighty-two (82) per cent. 01'' H SQ) and add two (2) parts of glycerin. Heat this mixture slowly to a temperature oi from one hundred to one hundred and ten degrees centigrade (100-110C.) and maintain this temperature until all the anthracene has gone into solution. Allow the mixture to cool, pour into water, add common salt, and filter off the condensation product, which when dry is a gray-green powder consisting, chiefly, of one part soluble in water and another part insoluble in water. This latter on being crystallized from alcohol can be obtained in the form of yellow needles, melting at a temperature of one hundred and seventy degrees centigrade (170C) and is the aforementioned compound, to which we have given the name benzanthrone. It dissolves in concentrated sulfuric acid, giving an orange-red solution with a fluorescence of thesamecolor. Onbeingmeltedwith'caustic alkali it yields a coloring-matterinsoluble in water, which, however, dissolves in alkaline hydrosulfite solution, yielding a vat which dyes vegetable fiber violet. The part of the raw product which is soluble in water also dissolves in concentrated sulfuric acid, giving an orange-red solution with a fluorescence of the same color. On melting with caustic alkali it gives rise to a coloring-matter similar to that obtained from the part insoluble in water. Instead of anthracene in this example derivativessuch, for example, as the anthracene sulfo acids-or homologues for example, niethylanthracenecan be success fully substituted.

Example 2: Suspend ten (10) parts of anthranol prepared according to the method of Liebermann and Gimbel (Berichte, Vol. XX, page 1854) in one hundred and fifty (150) parts of sulfuric acid (containing about eighty-two (82) per cent. of H 80 and add ten (10) arts of glycerin. Warm this mix ture care ully to a temperature of about one hundred and twenty degrees centigrades (120 C.) It begins to turn red, a fairly violent reaction sets in, and sulfur dioxid is evolved. When the reaction is ended, allow the melt to cool and then pour it into water, whereupon the reaction product separates out in olive-green flakes. Filter these off and wash, press, and dry. The'dried unpurified condensation product is a light olivegreen powder insoluble in dilute acids and alkalies. Concentrated sulfuric acid dissolves it, the solution being reddish brown with an intense orange-colored fluorescence. The greater part of it is soluble in alcohol and crystallizes out of this solution in slender light-yellow needles, which melt at a temperature of one hundred and seventy degrees centigrade, (170 C.) This is the same compound as that to which we have given the name benzanthrone, (of the preceding example 1.) These needles dissolvein concentrated sulfuric acid, the solution being brilliant orange red with a similar fluorescence. On melting these needles with caustic alkali an insoluble dyestuff is obtained which when reduced dies vegetable fiber violet. A similar product, which contains the above-mentioned compound, melting at a temperature of one hundred and seventy degrees centigrade (170 C.) is obtained when oxanthra- I101 is treated in a similar manner, while an- I thranol sulfo-acid yields a condensation product which is soluble in water, but which otherwise possesses similar properties.

Example 3: Thoroughly mix together one (1) part of anthranol, twenty (20) parts of glycerin, and five (5) parts of zinc chlorid and heat the mixture to a temperature of from two hundred and ten to two hundred and twenty degrees centigrade, (2 10220 C.) After a short time a test portion worked up with water and dissolved in concentrated sulfuric acid shows the orange color and fluorescence characteristic of benzanthrone. When .the reaction is complete, treat with hot water to remove the excess of glycerin and zinc chlorid and then purify the residue by means of crystallization. In this way benzanthrone is obtained.

Example 4: Dissolve ten (10) parts of the sodium salt of anthraquinone-beta-monosulfo-acid in one hundred and fifty (150) arts of sulfuric acid, (containing about eighty-two (82) per cent. of H Add twenty (20) parts of glycerin and warm care fully to a temperature of from one hundred and forty to one hundred and fifty degrees centigrade, (140150 C.) When the reaction is ended, allow the melt to cool, pour it into water, and salt out by means of common salt the condensation product which is soluble in water. The unpurified product is a dark powder which is fairly easily soluble in hot water, the solution being a pale olive brown which scarcely changes on the addition of alkali. The solution in concentrated sulfuric acid is orange brown and shows a strong green fluorescence. This condensation product on being melted with caustic potash also yields a dyestuff which after reduction dyes vegetable fiber violet.

Example 5: Heat together for a few hours in an autoclave at a temperature of about one hundred and fifty degrees centigrade (150 C.) one (1) part of anthranol sulfo-acid, (prepared by reducing anthraquinonebetamono-sulfo-acid with tin and hydrochloric acid,) two (2) parts of glycerin, and five (5) parts of fuming hydrochloric acid. After the melt has cooled dissolve in water, filter, and precipitate the benzanthrone sulfo-acid from the filtrate by means of common salt. The product so obtained possesses properties similar to those of the product obtained according to the foregoing example 4. Anthraquinone itself also yields similar condensation products, although the reaction does not proceed so easily. It can, however, be assisted by adding to the melt a reducing agent-such, for instance, as iron, iron sulfate, zinc, tin, or anilin sulfate.

Example 6: Suspend ten (10) parts of anthraquinone in four hundred (400) parts of sulfuric acid (containing about eighty-two (82) per cent. of ILSO and add twenty parts of glycerin and twenty (20) parts of anilin sulfate. Heat the mixture carefully to a temperature of from one hundred and thirty to one hundred and forty degrees een tigrade (1301&0 C.) and maintain this temperature until the reaction mixture has assumed a uniform brown-red color. Allow the melt to cool and pour it into water and work it up, which may be done after the usual manner of performing such operations. The condensation product obtained has the same appearance and possesses the same properties as that obtained according to the preceding example 2.

hat we claim is 1. The process for the production of new anthracene compounds called benzanthrones by condensing a hereinbefm'e defined anthraeene body free from nitrogen with glycerin.

2. The process for the production of new anthracene compounds called benzanthrones by condensing a h'ereinbeforc-delined anthracene body free from nitrogen with glycerin in the presence of sulfuric acid.

3. The process for the production of new anthraeene compounds called benzantln'ones by condensing oxanthranol with glycerin.

t. The process for the production of new anthracene compounds called benzanthrones by condensing oxanthrauol with glycerin in the presence of sulfuric acid.

As new articles of manufacture the anthracene compounds called benzanthrones such as can be obtained by condensing a hereinbefore-delined anthracene body with glycerin, which compounds dissolve in concentrated sulfuric acid yielding from orange to green solutions with green to red fluores cence, and which on melting with caustic alkali yield violet blue colorin gmatters which from an alkalinc-hydrosulfite vat dye vegetable fiber substantively.

6. As a new article of manufacture the anthracene compound called bcnzanthrone such as can be obtained by condensing OX" anthranol with glycerin, which compound dissolves in concentrated sulfuric acid giving an orange-red solution with an orange-red fluorescence, which is insoluble in water, and which on melting with caustic alkali yields a violet-blue coloring-inattcr which from an alkaline-hydrosullite vat dyes vegetable fiber sul )stantively.

In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

ROLAND HEINRICH SCHOLL. OSCAR BALLY.

\Vitnesses:

Enyns'r F. Emumno'r, Jos. H. LEU'IE. 

